Stochastic Binding Dynamics of a Photoswitchable Single Supramolecular Complex

In this work, a real‐time precise electrical method to directly monitor the stochastic binding dynamics of a single supramolecule based on the host‐guest interaction between a cyclodextrin and an azo compound is reported. Different intermolecular binding states during the binding process are distinguished by conductance signals detected from graphene‐molecule‐graphene single‐molecule junctions. In combination with theoretical calculations, the reciprocating and unidirectional motions in the trans form as well as the restrained reciprocating motion in the cis form due to the steric hindrance is observed, which could be reversibly switched by visible and UV irradiation. The integration of individual supramolecules into nanocircuits not only offers a facile and effective strategy to probe the dynamic process of supramolecular systems, but also paves the way to construct functional molecular devices toward real applications such as switches, sensors, and logic devices.